KR102486314B1 - Solvent-free thermosetting quantumdot resin composition, quantumdot resin composite prepared therefrom, led package and display device using the same - Google Patents

Abstract

The present invention relates to a solvent-free thermosetting quantumdot resin composition, a quantumdot resin composite prepared therefrom, and an LED package and display device using the same, and specifically, to a solvent-free thermosetting quantumdot resin composition having excellent ability to maintain optical properties even after long-term driving of a display, a quantumdot resin composite prepared therefrom, and an LED package and display device using the same.

Description

Solvent-free thermosetting quantum dot resin composition, quantum dot resin composite prepared therefrom, LED package and display device applying the same

The present invention relates to a non-solvent type thermosetting quantum dot resin composition, a quantum dot resin composite prepared therefrom, and an LED package and display device using the same, and specifically, a non-solvent type thermosetting quantum dot resin composition excellent in maintaining optical properties even after driving a display for a long time, from which It relates to a manufactured quantum dot resin composite, an LED package and a display device to which the same is applied.

Quantum dot (QD) is a so-called semiconductor nanocrystals, which can generate various colors by generating light of different wavelengths for each particle size without changing the type of material, and is said to have higher color purity and light stability than conventional light emitting materials. Due to its advantages, it is attracting attention as a next-generation light emitting device.

Displays using quantum dots that are currently on the market take the form of manufacturing a film containing quantum dots (QDs) and then embedding the film in a TV. When applied in the form of a film in this way, there is a disadvantage that the amount of quantum dots increases. When the above-described film-type quantum dots are converted and applied to an LED package display, the amount of quantum dots used can be significantly reduced, the thickness of the TV can be significantly reduced, and self-luminous properties like OLED TVs can be exhibited.

However, in the case of the LED package display, there is a problem in that the thermal resistance of the package is high, thereby reducing the lifespan and reducing reliability. Therefore, there was a prior art (Publication No. 10-2018-0061146) that improved color reproducibility and durability by using organic compounds and inorganic phosphors instead of quantum dots that were vulnerable to heat and moisture, etc., and synthesized quantum dots with a continuous crystal growth structure and the surface of the quantum dots. A prior art (Publication No. 10-2018-0097201) in which a metal oxide film was formed to improve the thermal stability of quantum dots has been disclosed.

However, it is difficult to solve this problem simply by improving heat resistance, and therefore, in order to apply quantum dots to LED package displays, a quantum dot resin composition or a quantum dot composite having excellent durability and reliability is required.

As an encapsulant for protecting LED chips, thermoplastic resins or thermosetting resins have been used, but as LEDs develop to high output, thermosetting resins with better heat resistance and light resistance have been widely used.

Conventionally, an alicyclic epoxy or polysiloxane was used as such a thermosetting resin, but when the LED package display was used for a long time, it was found that a decrease in brightness or a change in chromaticity occurred in terms of light characteristics such as brightness and chromaticity. In addition, even though isocyanurate or nanosilica materials were mixed and used to improve the heat resistance of the alicyclic epoxy, the problem of deterioration in optical properties could not be solved.

Accordingly, the problem to be solved by the present invention is to provide a solvent-free thermosetting quantum dot resin composition having improved light stability and improved reliability, a quantum dot resin composite prepared therefrom, and an LED package and display device using the same.

According to one aspect of the present invention for solving the above problems, including a quantum dot, an epoxy resin, an acid anhydride curing agent and a curing accelerator,

The epoxy resin provides a solvent-free thermosetting quantum dot resin composition, characterized in that it comprises a dicyclopentadiene (dicyclopentadiene) type epoxy resin.

Preferably, the epoxy resin provides a solvent-free thermosetting quantum dot resin composition, characterized in that it further comprises triglycidyl isocyanurate.

Preferably, the dicyclopentadiene (dicyclopentadiene) type epoxy resin provides a solvent-free thermosetting quantum dot resin composition, characterized in that it contains a (meth) acrylate functional group.

Preferably, the epoxy resin and the acid anhydride curing agent are included in a weight ratio of 1:0.5 to 1:1.4 to provide a solvent-free thermosetting quantum dot resin composition.

Preferably, a non-solvent type thermosetting quantum dot resin composition is provided, characterized in that the retention rate of optical properties calculated by Equation 1 below is 80% or more.

[Equation 1]

Optical characteristic retention rate (%) = (Light characteristic after 1,000 hours of display driving / Display optical characteristic before driving) X 100

Preferably, the quantum dots are 1 to 30 parts by weight,

The epoxy resin is 1 to 50 parts by weight,

1 to 50 parts by weight of the acid anhydride curing agent and

The curing accelerator provides a non-solvent type thermosetting quantum dot resin composition, characterized in that it comprises 0.05 to 1 part by weight.

Preferably, the epoxy resin,

At least one selected from the group consisting of alicyclic epoxy resins, BPA-PO epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, novolac-type epoxy resins, nitrogen-containing epoxy resins, linear aliphatic epoxy resins, and naphthalene-type epoxy resins It provides a solvent-free thermosetting quantum dot resin composition, characterized in that it further contains.

Preferably, the acid anhydride curing agent,

Phthalic anhydride, maleic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, methyl It provides a non-solvent type thermosetting quantum dot resin composition, characterized in that at least one selected from the group consisting of hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride.

Preferably, the curing accelerator,

It provides a non-solvent type thermosetting quantum dot resin composition, characterized in that at least one selected from the group consisting of tertiary amines, imidazole compounds, quaternary phosphonium salts, organometallic salts and phosphorus compounds.

Preferably, it further comprises an inorganic filler,

The inorganic filler is a non-solvent type thermosetting quantum dot resin composition, characterized in that at least one selected from the group consisting of silica, zinc oxide, alumina, calcium carbonate, barium carbonate, barium sulfate, zinc sulfate, zinc sulfide, magnesium oxide and antimony oxide provides

In another aspect of the present invention, a quantum dot resin composite prepared from the solvent-free thermosetting quantum dot resin composition is provided.

In another aspect of the invention, the LED chip and

It is formed on the LED chip and provides an LED package including a light conversion layer made of the solvent-free thermosetting quantum dot resin composition.

In another aspect of the present invention, a display device including the LED package is provided.

The solvent-free thermosetting quantum dot resin composition and the quantum dot resin composite prepared therefrom according to the present invention have excellent durability, and when applied to LED packages and display devices, maintain optical properties even after long-term use.

In addition, the non-solvent type thermosetting quantum dot resin composition according to the present invention has excellent miscibility between quantum dots and resin without including a solvent and can realize various viscosities, so that display devices can be manufactured under various process conditions.

Hereinafter, the present invention will be described.

All terms (including technical and scientific terms) used in this specification, unless otherwise defined, may be used in a meaning commonly understood by those of ordinary skill in the art to which the present invention belongs. In addition, terms defined in commonly used dictionaries are not interpreted ideally or excessively unless explicitly specifically defined.

In addition, throughout this specification, when a certain component is said to "include", it means that it may further include other components, not excluding other components, unless otherwise stated.

In addition, throughout this specification, optical characteristics include brightness (Lv) and chromaticity (Cx, Cy) of a display.

<Solvent-free thermosetting quantum dot resin composition>

The quantum dot resin composition according to an embodiment of the present invention is a non-solvent type thermosetting quantum dot resin composition, specifically, it has excellent miscibility between quantum dots and resin without including a solvent and can realize various viscosities, so that it can be used for display devices under various process conditions. can be manufactured

For example, a non-solvent type thermosetting quantum dot resin composition including a quantum dot, an epoxy resin, an acid anhydride curing agent and a curing accelerator, and the epoxy resin including a dicyclopentadiene (DCPD) type epoxy resin is provided.

When the dicyclopentadiene-type epoxy resin is included, it has high durability and is excellent in maintaining optical properties even after long-term use. In addition, even when triglycidyl isocyanurate is further included in the dicyclopentadiene-type epoxy resin, an effect of maintaining optical properties after long-term use can be obtained.

Preferably, when a (meth)acrylate functional group is further included in the dicyclopentadiene type epoxy resin, it can have high adhesiveness and excellent barrier properties (resistance to moisture absorption), resulting in better durability, thereby improving optical properties even after long-term use. this is well maintained In addition, since it may have a low viscosity characteristic, it is possible to evenly disperse the quantum dots without including a solvent and realize various viscosities.

The quantum dot resin composition according to an embodiment of the present invention may further include an inorganic filler to impart thixotropic properties.

The quantum dot resin composition according to an embodiment of the present invention may include 1 to 30 parts by weight of quantum dots, 1 to 50 parts by weight of an epoxy resin, 1 to 50 parts by weight of an acid anhydride curing agent, and 0.05 to 1 part by weight of a curing accelerator.

The quantum dot resin composition according to an embodiment of the present invention contains 1 to 30 parts by weight of quantum dots, 1 to 50 parts by weight of an epoxy resin, 1 to 50 parts by weight of an acid anhydride curing agent, 0.05 to 1 part by weight of a curing accelerator, and 0.1 to 20 parts by weight of an inorganic filler. It can be included in parts by weight.

Hereinafter, the composition of the non-solvent type thermosetting quantum dot resin composition of the present invention will be described in detail.

epoxy resin

In the present invention, the epoxy resin preferably necessarily includes a dicyclopentadiene (DCPD) type epoxy resin, and may further include triglycidyl isocyanurate (TGIC). In addition, the dicyclopentadiene (DCPD) type epoxy resin may include a (meth)acrylate functional group. "(meth)acrylate" refers to acrylate and methacrylate.

The DCPD-type epoxy resin is an epoxy resin derived from dicyclopentadiene, and refers to an epoxy resin having two or more epoxy groups per molecule.

When the DCPD type epoxy resin is included, it has good adhesive strength and excellent barrier properties, thereby preventing external air and moisture from penetrating into the quantum dot resin composition, thereby improving durability and maintaining optical properties of the quantum dot resin composition. Furthermore, when a DCPD-type epoxy resin containing at least one (meth)acrylate functional group is used, adhesive strength and barrier properties are further improved, and accordingly, the retention rate of optical properties is greatly improved. This seems to be because, in addition to curing between the epoxy group and the curing agent, curing by the (meth)acrylate functional group is added to form a more complex and dense three-dimensional network structure.

Triglycidyl Isocyanurate (TGIC) can be cured in three directions and has excellent mechanical strength and heat resistance, as well as good adhesion and high-temperature performance. Therefore, when used together with DCPD-type epoxy resin, it seems to have an effect of improving the retention rate of optical properties by helping to improve adhesive strength and barrier properties. Although not described as a comparative example in the present specification, light stability was relatively excellent when TGIC epoxy was applied, compared to adding bisphenol A type epoxy or alicyclic epoxy to DCPD type epoxy resin.

In addition, depending on the required physical properties such as heat resistance and chemical resistance, alicyclic epoxy resins, BPA-PO epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolak type epoxy resins, nitrogen-containing epoxy resins, linear aliphatic epoxy resins and naphthalene It may further include one or more selected from the group consisting of type epoxy resins. For example, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, or novolac-type epoxy resin may be added to enhance chemical resistance and heat resistance, and alicyclic epoxy resin and the like may be added to enhance weather resistance and tracking resistance. can be added. BPA-PO epoxy resin can be used for flexibility of the cured product, linear aliphatic epoxy resin can be used to increase mobility by realizing low viscosity, and naphthalene type epoxy resin can be used for low thermal expansion and moisture absorption resistance. .

The total content of the epoxy resin in the quantum dot resin composition may be 1 to 50 parts by weight, preferably 20 to 50 parts by weight, more preferably 35 to 45 parts by weight. If the content of the epoxy resin is less than 1 part by weight, mechanical properties of the cured product may be deteriorated, and if it is greater than 50 parts by weight, optical properties of the display may be deteriorated.

The epoxy resin and the acid anhydride curing agent may be included in a weight ratio of 1:0.5 to 1:1.4, preferably 1:0.75 to 1:1.2, and more preferably 1:0.9 to 1:1.0. may be included in weight ratio. When the epoxy resin and the acid anhydride curing agent are included in the above weight ratio, the retention rate of optical properties is improved, and especially the retention rate of brightness (Lv) is greatly improved.

acid anhydride curing agent

In the present invention, the acid anhydride curing agent reacts with the epoxy resin to form a three-dimensional network structure, resulting in excellent mechanical properties of the cured product. Just as the properties of an epoxy resin affect the properties of the composition or final cured product, the properties of the curing agent used also affect the properties of the composition or final cured product. When a curing agent is used, heat resistance is excellent.

In the present invention, the acid anhydride curing agent is phthalic anhydride, maleic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, It may be at least one selected from the group consisting of diethylglutaric anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

In the quantum dot resin composition, the content of the acid anhydride curing agent may be 1 to 50 parts by weight, preferably 20 to 50 parts by weight, and more preferably 35 to 45 parts by weight. If the content of the acid anhydride curing agent is less than 1 part by weight, curing of the epoxy resin may be delayed or may not be sufficiently cured, and if it exceeds 50 parts by weight, there is no benefit due to the excess content and the optical properties of the display may be deteriorated.

hardening accelerator

The curing accelerator according to the present invention serves to accelerate the curing reaction between the epoxy resin and the acid anhydride curing agent. Specifically, at least one selected from the group consisting of tertiary amines, imidazole compounds, quaternary phosphonium salts, organometallic salts, and phosphorus compounds may be used.

In the quantum dot resin composition, the content of the curing accelerator may be 0.05 to 1.0 parts by weight, preferably 0.05 to 0.5 parts by weight, more preferably 0.08 to 0.2 parts by weight. If the content of the curing accelerator is less than 0.05 parts by weight, a sufficient curing accelerating effect may not be obtained, and if it exceeds 1.0 parts by weight, discoloration may appear in the cured product.

quantum dot

Quantum Dot (QD) is a nano-sized semiconductor material, and may have different energy band gaps depending on its size and composition, and thus emit light of various emission wavelengths.

These quantum dots have a homogeneous monolayer structure; a multilayer structure such as a core-shell type, a gradient structure, and the like; or a mixture thereof. When the shell has multiple layers, each layer may contain components different from each other, such as (semi)metal oxides.

The quantum dot (QD) may be freely selected from a group II-VI compound, a group III-V compound, a group IV-VI compound, a group IV element, a group IV compound, and combinations thereof. When the quantum dot is in the core-shell form, the core and the shell may be freely composed of the components exemplified below, respectively.

In one example, the II-VI compound is a binary element compound selected from the group consisting of CdO, CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, MgSe, MgS, and mixtures thereof; A ternary selected from the group consisting of CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, MgZnSe, MgZnS and mixtures thereof bovine compounds; and CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and quaternary compounds selected from the group consisting of mixtures thereof.

In another example, the group III-V compound is a binary element compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; A ternary compound selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, and mixtures thereof; And it may be selected from the group consisting of quaternary compounds selected from the group consisting of GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. there is.

In another example, the group IV-VI compound is a binary compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; a ternary compound selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; And it may be selected from the group consisting of quaternary compounds selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof.

In another example, the group IV element may be selected from the group consisting of Si, Ge, and mixtures thereof. The group IV compound may be a binary element compound selected from the group consisting of SiC, SiGe, and mixtures thereof.

The above-mentioned two-element compound, three-element compound, or quaternary element compound may be present in the particle at a uniform concentration, or may be present in the same particle in a state in which the concentration distribution is partially different. Also, one quantum dot may have a core/shell structure surrounding another quantum dot. The interface between the core and the shell may have a concentration gradient in which the concentration of elements present in the shell decreases toward the center.

The shape of the quantum dot is not particularly limited as long as it is a shape commonly used in the art. For example, spherical, rod-shaped, pyramidal, disc-shaped, multi-arm, or cubic nanoparticles, nanotubes, nanowires, nanofibers, nanoplatelet particles etc. can be used.

In addition, the size of the quantum dots is not particularly limited and may be appropriately adjusted within a common range known in the art. For example, the average particle diameter (D ₅₀ ) of the quantum dots may be about 2 to 10 nm. In this way, when the particle diameter of the quantum dots is controlled to be in the range of about 2 to 10 nm, light of a desired color can be emitted. For example, when the particle diameter of the quantum dot core/shell containing InP is about 5 to 6 nm, light having a wavelength of about 520 to 550 nm can be emitted, while the particle diameter of the quantum dot core/shell containing InP is about In the case of 7 to 8 nm, light of about 620 to 640 wavelengths can be emitted. For example, as the blue-emitting QD (Quantum dot), a non-cadmium (Cd) group III-V QD (eg, InP, InGaP, InZnP, GaN, GaAs, GaP) can be used.

In the present specification, the quantum dot may include one or more selected from the group consisting of the above-described quantum dot nanoparticles, quantum dot-containing particles, primary particles in which a plurality of quantum dot particles are bonded, and quantum dot composite particles.

For example, the quantum dot-containing particle may be a particle containing at least one quantum dot, and specifically include at least one quantum dot particle bonded to the surface of an inorganic core particle or a polymer core particle.

For another specific example, the primary particle may be a particle in which a plurality of quantum dots are aggregated or a particle in which a plurality of quantum dots are embedded in a matrix. Such matrices may be conventional inorganic or organic materials known in the art.

The primary particles may further include conventional thermally conductive inorganic particles known in the art. These inorganic particles play a role in releasing self-heating of quantum dots to the outside due to their excellent thermal conductivity.

Non-limiting examples of usable thermally conductive inorganic particles include aluminum oxide, silicon oxide, titanium dioxide, aluminum nitride, boron nitride, silicon nitride, silicon carbide, aluminum oxide, or a mixture of two or more.

The average particle diameter (D ₅₀ ) of the thermally conductive inorganic particles is not particularly limited and may be appropriately adjusted within a range known in the art. For example, the average particle diameter of the thermally conductive inorganic particles may be 1 to 100 μm, specifically 1 to 50 μm. At this time, two or more types of thermally conductive inorganic particles having different average particle diameters or different components may be mixed.

The content of these thermally conductive inorganic particles is not particularly limited and may be appropriately adjusted in consideration of exothermic properties.

For example, the content of the thermally conductive inorganic particles may be 0.1 to 99.9 parts by weight, specifically 0.5 to 99.5 parts by weight, based on the total weight (eg, 100 parts by weight) of the primary particles. In addition, the thermally conductive inorganic particles may be 1 to 100,000 parts by weight, specifically 100 to 100,000 parts by weight based on 100 parts by weight of the mixed quantum dots.

The quantum dot composite particle may include a surface treatment layer containing at least one of a halide and an oxyhalide between the quantum dots and the polymer coating layer. For a specific example, quantum dots; (oxy) halide surface treatment layer bonded to the surface of the quantum dots; And the (meth) acrylic polymer coating layer may be sequentially formed.

The surface treatment layer may include a halogen (X = F, Cl, Br, I)-containing material known in the art without limitation, and may be, for example, a halogen salt of at least one of fluoride, chloride, bromide, and iodide. there is. Specifically, it may include an organic halide, an inorganic halide, an inorganic oxyhalide, or a combination thereof.

Non-limiting examples of halogen-containing materials that can be used are tetrabutylammonium bromide, cetyltrimethylammonium bromide, cetyl ammonium bromide (CTAB: Cetyl Ammonium Bromide), ammonium chloride, ammonium bromide, ammonium iodide, ammonium fluoride, potassium Chloride, potassium bromide, potassium iodide, sodium chloride, sodium bromide, sodium iodide, indium chloride, indium bromide, indium iodide and the like. The above components may be used alone or in combination of two or more.

As the polymer, a conventional acrylic or methacrylic polymer known to sugar molecules may be used without limitation, and specifically, it is preferable to use a (meth)acrylic polymer containing a polar functional group within a predetermined range.

For example, the (meth)acrylic polymer has a content of at least one polar functional group selected from a carboxyl group and a hydroxyl group in a molecule of 1 part by weight or more, specifically 1 to 50 parts by weight, and a molecular weight (Mw) of 5,000 g/mol Above, specifically, 10,000 to 500,000 g/mol of a (meth)acrylic monomer polymer or (meth)acrylic resin may be used.

For the quantum dots used in the present invention, reference may be made to Publication No. 10-2021-0033160 to the extent not contradicted by the present specification.

In the quantum dot resin composition, the content of the quantum dots may be 1 to 30 parts by weight, preferably 5 to 25 parts by weight, and more preferably 10 to 20 parts by weight. If the content of the quantum dots exceeds 30 parts by weight, application characteristics and optical characteristics may be deteriorated.

inorganic filler

In the present invention, the inorganic filler can be used together with an epoxy resin and an acid anhydride curing agent to improve mechanical properties such as reduction of thermal expansion rate and curing shrinkage of the composition or final cured product, improve adhesion, and impart thixotropy to the composition. can

In the present invention, the inorganic filler may be selectively used depending on the required process. Specifically, in order to apply the quantum dot resin composition according to the present invention in a dome shape on an LED chip, it may be used to impart thixotropy to the composition.

The usable inorganic filler may be at least one selected from the group consisting of silica, zinc oxide, alumina, calcium carbonate, barium carbonate, barium sulfate, zinc sulfate, zinc sulfide, magnesium oxide and antimony oxide.

When the inorganic filler is included in the quantum dot resin composition, the amount thereof may be 0.1 to 20 parts by weight, preferably 0.1 to 15 parts by weight, and more preferably 0.1 to 10 parts by weight. If the content of the inorganic filler exceeds 20 parts by weight, coating properties may be deteriorated.

Properties

The quantum dot resin composition according to the present invention has an optical property retention rate of 80% or more, preferably 90% or more, in terms of brightness (Lv) and color coordinates (Cx, Cy). The optical property retention rate is calculated by Equation 1 below.

Equation 1

Optical characteristic retention rate (%) = (Light characteristic after 1,000 hours of display driving / Display optical characteristic before driving) X 100

Manufacturing method of quantum dot resin composition

The quantum dot resin composition according to the present invention may be prepared by mixing an epoxy resin, an acid anhydride curing agent, a curing accelerator, and quantum dots at room temperature. In addition to this for imparting thixotropic properties, it may be prepared by mixing together an inorganic filler.

<Quantum dot resin composite, LED package and display device>

On the other hand, the present invention provides a quantum dot resin composite prepared from the above-described solvent-free thermosetting quantum dot resin composition.

In addition, the present invention provides an LED package, which includes an LED chip and a light conversion layer formed on the LED chip and made of the above-described solvent-free thermosetting quantum dot resin composition.

In addition, the present invention provides a display device including the above-described LED package.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only for exemplifying the present invention, and the scope of the present invention is not limited to the examples.

Example 1

Epoxy resin 1 (EP-4088S, ADEKA), acid anhydride curing agent (methylhexahydrophthalic anhydride, MH-700G, New Japan Chemical), curing accelerator (quaternary phosphonium salt), inorganic filler (SiO ₂ , EVONIK) and chloride A non-solvent type thermosetting quantum dot resin composition was prepared by mixing quantum dot composite particles surface-treated with (chloride) (according to Example 1 of Publication No. 10-2021-0033160). Epoxy resin 1 is a DCPD type epoxy resin and contains a methacrylate functional group. Each composition ratio is shown in Table 1 below.

Example 2 and Example 3

It was prepared in the same manner as in Example 1, except that the contents of epoxy resin 1 and acid anhydride curing agent were changed.

Example 4 and Example 5

Epoxy resin 1 and epoxy resin 2 (TGIC, TEPIC-S, Nissan Chemical) were prepared in the same manner as in Example 1, except that the composition ratios were mixed and used.

Comparative Example 1 and Comparative Example 2

Epoxy Resin 2 and Epoxy Resin 3 (C-2021P, Daicel Corporation) were prepared in the same manner as in Example 1, except that each composition ratio was mixed and used. Epoxy resin 3 is one of alicyclic epoxies, and is 3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate.

<Evaluation of optical characteristics (Lv, Cx, Cy) retention ability>

After applying the quantum dot resin composition prepared in Examples 1 to 5 and Comparative Examples 1 to 2 to the LED chip on the PCB substrate, it was cured at about 190 ° C. for about 5 minutes to manufacture a display device. By measuring the initial optical characteristic values (Lv, Cx, Cy) and the optical characteristic values after driving for 1,000 hours of the manufactured display device using the optical spot characteristic measuring device (CA410), the optical characteristic retention rate according to the values is calculated in Equation 1 below. calculated according to The results are shown in Table 2.

Equation 1

Optical characteristic retention rate (%) = (Light characteristic after 1,000 hours of display driving / Display optical characteristic before driving) X 100

Comparing Examples 1 to 5 with Comparative Examples, Comparative Examples had poor optical property retention rates compared to Examples 1 to 5 in all of the optical properties (Lv, Cx, Cy), and in particular, the Lv and Cy items showed remarkable physical properties. It wasn't good. On the other hand, Examples 1 to 5 showed a retention rate of 80% or more in all items, and excellent retention rates of 90% or more in most examples.

In Examples 1 to 5, the higher the DCPD type epoxy resin ratio, the better the optical property retention rate, and when only the DCPD type epoxy resin was used as in Examples 1 to 3, the Lv retention rate was 99% or more.

With respect to Examples 1 to 3, when the weight ratio of the epoxy resin and the curing agent was about 1:0.94 (Example 1), the retention rate was better in all items.

It is obvious to those skilled in the art that the present invention is not limited to the above embodiments and can be variously modified or modified without departing from the technical gist of the present invention. it did

Claims (13)

Including quantum dots, epoxy resins, acid anhydride curing agents and curing accelerators,
The epoxy resin is a non-solvent type thermosetting quantum dot resin composition, characterized in that it comprises a dicyclopentadiene (dicyclopentadiene) type epoxy resin. The method of claim 1,
The epoxy resin is a non-solvent type thermosetting quantum dot resin composition, characterized in that it further comprises triglycidyl isocyanurate (Triglycidyl Isocyanurate). The method of claim 1,
A non-solvent type thermosetting quantum dot resin composition, characterized in that the dicyclopentadiene (dicyclopentadiene) type epoxy resin contains a (meth) acrylate functional group. The method of claim 1,
The epoxy resin and the acid anhydride curing agent is characterized in that contained in a weight ratio of 1: 0.5 to 1: 1.4, solvent-free thermosetting quantum dot resin composition. The method of claim 1,
A non-solvent type thermosetting quantum dot resin composition, characterized in that the retention rate of optical properties calculated by Equation 1 below is 80% or more.
[Equation 1]
Optical characteristic retention rate (%) = (Light characteristic after 1,000 hours of display driving / Display optical characteristic before driving) X 100 The method of claim 1,
1 to 30 parts by weight of the quantum dots,
The epoxy resin is 1 to 50 parts by weight,
1 to 50 parts by weight of the acid anhydride curing agent and
The curing accelerator is a non-solvent type thermosetting quantum dot resin composition, characterized in that it comprises 0.05 to 1 part by weight. The method according to claim 1, wherein the epoxy resin,
At least one selected from the group consisting of alicyclic epoxy resins, BPA-PO epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, novolac-type epoxy resins, nitrogen-containing epoxy resins, linear aliphatic epoxy resins, and naphthalene-type epoxy resins A non-solvent type thermosetting quantum dot resin composition, characterized in that it is further included. The method according to claim 1, wherein the acid anhydride curing agent,
Phthalic anhydride, maleic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, methyl A non-solvent type thermosetting quantum dot resin composition, characterized in that at least one selected from the group consisting of hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride. The method according to claim 1, wherein the curing accelerator,
A non-solvent type thermosetting quantum dot resin composition, characterized in that at least one selected from the group consisting of tertiary amines, imidazole compounds, quaternary phosphonium salts, organometallic salts and phosphorus compounds. The method of claim 1,
Including more inorganic fillers,
The inorganic filler is a non-solvent type thermosetting quantum dot resin composition, characterized in that at least one selected from the group consisting of silica, zinc oxide, alumina, calcium carbonate, barium carbonate, barium sulfate, zinc sulfate, zinc sulfide, magnesium oxide and antimony oxide . A quantum dot resin composite made of the non-solvent type thermosetting quantum dot resin composition according to any one of claims 1 to 10. LED chips; and
A light conversion layer formed on the LED chip and made of the solvent-free thermosetting quantum dot resin composition according to any one of claims 1 to 10: A LED package comprising a. A display device comprising the LED package according to claim 12.